JP3500237B2 - Pressing and cleaning rust preventive oil composition for cold rolled steel sheet and galvanized steel sheet - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lubricating oil composition for preparing a cleaning rust preventive oil used in the automobile industry, the home appliance industry and the like.

More specifically, cold-rolled steel sheets and galvanized steel sheets (electroplating, hot dipping, alloying plating, alloy-plating steel sheets, etc.) manufactured by steel makers are press-formed into automobile parts, home electric appliance parts, etc. To save
Used as a cleaning rust preventive oil for the purpose of cleaning steel sheets and rust prevention of molded parts, it can also be used as it is in the forming press working process of cold-rolled steel sheets and galvanized steel sheets. The present invention relates to a rust preventive oil composition.

[0003]

[Prior art]

1. Background Cold-rolled steel sheets have hitherto been used as materials for automobile bodies, home electric appliances, and the like. However, in recent years, mainly in the automobile industry, improvement in corrosion resistance and rust prevention of vehicle bodies and parts themselves has been demanded. For this reason, cold-rolled steel sheets are electroplated (electrogalvanized, electrogalvanized alloy plated), hot-dipped (hot-dip galvanized, hot-dip galvannealed, double-layered hot-dip galvanized, etc.) and organically coated. Surface-treated steel sheets, especially galvanized steel sheets, are widely used. Furthermore, recently, the thickness of galvanized steel sheets has been further increased.

By the way, cold rolled steel sheets and galvanized steel sheets are coated with rust preventive oil for steel plates (rust preventive oil for shipping) at the stage of shipment from steel manufacturers and supplied to the automobile industry, home appliance industry and the like. . This rust preventive oil for steel sheet is focused on the rust preventive property during the storage period of the steel plate and before starting the steel plate cleaning process in the automobile / home appliance industry, etc., the oil stain preventive property in the laminated state, and the degreasing property. There is.

In order to meet these required performances, and in addition to this, from the viewpoints of economic efficiency by taking out oil and workability during handling, the rust preventive oil for steel sheet has a viscosity of 30 mm ^{2 at} 40 ° C. / S or less is required (see, for example, Japanese Patent Application Laid-Open No. 4-275399 related to the applicant's previous proposal). However, if the viscosity is too low, the thickness of the oil film after oiling becomes thin, which adversely affects the rust prevention property. Therefore, the lower limit of the viscosity of the rust preventive oil for steel sheet is set to 10 mm ² / s at 40 ° C.

Incidentally, there has been proposed a rust preventive oil for steel plates obtained by imparting press workability (lubricity in a forming press working process) to rust preventive oil for steel plates (rust preventive oil for shipping). However, if dust that adheres to the steel plate is washed with cleaning rust preventive oil at the stage of delivery to automobile manufacturers, most of the rust preventive oil for steel plate that was applied to the steel plate will be washed away with the dust. Get lost. In addition, rust preventive oil for steel plate and rust preventive oil for cleaning
Uses and performance requirements differ. Therefore, it is difficult to use the rust preventive oil for steel plates (rust preventive oil for shipping) as it is as the rust preventive oil for cleaning. 2. General performance of anti-rust oil for cleaning Cold-rolled steel sheets and galvanized steel sheets supplied from steel manufacturers are washed with anti-rust oil for cleaning before entering the forming / pressing process of automobile / home appliance parts.

[0007] Dust and chips during shirring adhere to the surfaces of cold-rolled steel sheets and galvanized steel sheets delivered to the automobile / home appliance industry and the like. If these dusts and chips are attached, small scratches will be applied during molding and the finish of the coated surface will be poor.

Therefore, the general performance of the rust preventive oil for cleaning is that these dusts and chips can be easily cleaned, and further, the rust preventive property and discoloration preventive property of the molded and pressed parts are
Degreasing properties and oil bleeding prevention properties in chemical conversion and painting processes are required. 3. Background of the development of rust preventive oil for press working and cleaning In recent years, steel manufacturers have been promoting the thickening of galvanized steel sheets in order to meet the demand from the automobile industry and the home appliance industry to improve the durability of galvanized steel sheets themselves. Has been.

However, for example, the recent alloyed hot-dip galvanized steel sheet is a difficult-to-work material as compared with the conventional cold-rolled steel sheet, so that press cracks, nicks and the like are likely to occur during the forming / pressing process step. , Productivity is decreasing. Therefore, in order to improve the productivity of alloyed hot-dip galvanized steel sheets and the like, and to expand the applications of surface-treated steel sheets, steel manufacturers have added press workability to cleaning rust preventive oil, Development of rust preventive oil for press working and cleaning is required.

Further, development of a rust preventive oil for press working and cleaning is also demanded by the automobile industry and the home appliance industry.

In particular, in the recent automobile industry, in order to simplify the forming / pressing process of a vehicle body or the like, parts having a complicated shape are formed by integral molding.

Therefore, the conventional rust preventive oil for cleaning cannot be used alone, and the viscosity at 40 ° C. is 50 to 100 mm ² /
In some cases, a highly viscous press oil of s may be used. Addition of such a high-viscosity press oil exerts adverse effects not only on rust resistance, economy, workability, but also on degreasing property and discoloration specific to galvanized steel sheet.

In addition, body manufacturers are rapidly introducing large-scale presses such as transfer presses and adopting thick-galvanized steel sheets.

[0014] Therefore, according to the knowledge about the conventional rust preventive oil for cleaning, not only cleaning property, rust preventive property and degreasing property but also press workability (lubricity at the time of molding press work) cannot be taken. The current situation is that it has come up to now. 4. Conventional technology relating to rust preventive oil for press working and cleaning At present, there is no rust preventive oil for cleaning for galvanized steel sheets that is on the market and has sufficient performance as a rust preventive oil for press working. The conventional base oil composition and additive composition of the cleaning rust preventive oil have only a slight oily effect, and a sufficient lubricating effect at the time of press working cannot be expected.

Further, recently, a rust preventive oil for cleaning which has a press workability is commercially available, but this has not yet reached sufficient performance.

For example, a commercially available oil containing an active type sulfur extreme pressure agent is extremely inferior in oil stain preventive property in a single plate or laminated state. Further, in a commercially available oil containing a certain type of sulfur-based extreme pressure agent, there is a problem in selection and blending ratio of other additives, and deterioration in atmospheric exposure performance and degreasing performance is recognized.

[0017]

In order to satisfy the general performance as a rust preventive oil for cleaning, from the viewpoints of cleanability, rust preventive property, discoloration preventive property, degreasing property, economical efficiency and workability, the product viscosity at 40 ° C. 10 mm ² / than must presser down.

Under such a low viscosity property, the thickening effect of the base oil composition and the rust preventive agent cannot be expected, and the thickness of the oil film remains thin. In order to impart press workability, various extreme pressure additives (chlorine, phosphorus, sulfur,
Hereinafter, such as organic molybdenum is referred to as "extreme pressure agent". ) May be added.

However, these extreme pressure agents have many active types, and if they do not have the correct selection and compounding composition, oil stains on the surface of cold rolled steel sheet or galvanized steel sheet, discoloration, extreme deterioration of degreasing performance, etc. Will cause trouble.

Further, the press workability of the galvanized steel sheet is as follows: Adhesive wear resistance of a soft pure plated material having a plated coating, peeling (powdering, flaking) prevention of an alloyed material having a hard coating, Due to the prevention of press cracking caused by various types of thick plated materials, there is a demand for better lubrication performance during molding and pressing.

The present invention provides a lubrication for preparing an anticorrosive oil for press working and washing, which is obtained by imparting press working performance (lubrication performance during forming press working) to cleaning rustproofing oil for cold-rolled steel sheets and galvanized steel sheets. It is intended to provide an oil composition.

In particular, the present invention provides a rust preventive oil composition for cold pressing and galvanizing, which has a good balance of rust preventive performance, degreasing performance, press working performance, etc. for cold working and cleaning. To aim.

[0023]

SUMMARY OF THE INVENTION Under the proposition that the product viscosity of cleaning rust preventive oils must be kept below 10 mm ² / s at 40 ° C., the present inventors have made various additions compatible therewith. The best combination in terms of the balance of rust prevention performance, discoloration prevention performance, degreasing performance and press processing performance, by searching for agents and examining the selection and combination of inert type extreme sulfur pressure agents and highly basic sulfonates. As a result of repeated experiments and studies for finding the amount, new knowledge was obtained and the present invention could be completed. (1) New findings The present inventors obtained the following new findings in the course of research. (A) Knowledge regarding the satisfaction of the three performances of rust prevention performance, degreasing performance, and press working performance The basic performance required for rust preventive oil for press working and washing for cold-rolled steel sheets and galvanized steel sheets is rust prevention performance, degreasing performance. Performance and press processing performance. However, these performances are fundamentally conflicting with each other.

Therefore, in order to satisfy all of these performances, the point is to select an appropriate additive and mix these in a well-balanced manner so that the additive and synergistic effects thereof are exerted. Become.

As the main component, a base oil, an anticorrosive additive, an inert type sulfur extreme pressure agent and a highly basic sulfonate are necessary, and a degreasing aid, an antioxidant, a pour point depressant, etc. as auxiliary components. Can be considered.

Particularly, in the inert type sulfur-based extreme pressure agent, the kind of sulfur-bonding compound and the content of active sulfur are important. Further, for the highly basic sulfonate, the total base number and the type of alkaline earth metal are important.

The present inventors have found that the above basic performance can be sufficiently achieved by appropriately selecting the types and blending amounts of the inert type sulfur extreme pressure agent and the highly basic sulfonate. (B) Findings regarding press cracking prevention property and plating layer peeling prevention property
In the case of a pure plated material having a soft plated layer, press cracking occurs due to adhesive wear. Further, in the case of an alloyed material having a hard plating layer, the plating layer peels off.

The inventors of the present invention have found that the inert type sulfur-based extreme pressure agent and the highly basic sulfonate also have the optimum compounding amounts with respect to the press cracking prevention property and the plating layer peeling prevention property. .

In deep drawing, press cracking occurs as the processing speed decreases. And the pure plated material is
Compared to alloyed materials, adhesive wear is more likely to occur and press cracking occurs. It is considered that this phenomenon occurs because the effect of drawing the lubricant to the processed surface is smaller as the processing speed becomes lower.

On the contrary, the alloyed material causes the peeling of the plating layer (powdering, flaking) as the processing speed becomes higher than that of the pure plated material. It is considered that this is because the plating film of the alloyed material has poor adhesion as compared with the plating film of the pure plating material and cannot follow the processing speed.

Further, in a high temperature experiment of a jig / steel plate assuming continuous pressing in an actual line, the working performance generally tends to decrease. It has been found that the workability is improved at a temperature higher than room temperature depending on the selection and the optimum composition. this is,
It is considered that the reactivity of the inactive type sulfur extreme pressure agent is activated by the temperature.

As described above, when considering a high-speed press line centering on the recent automobile industry, press cracking prevention property,
From the balance of the peeling prevention property of the plating layer, it was confirmed that the combination of the inert type extreme sulfur pressure agent and the highly basic sulfonate had the optimum value. (C) Knowledge on white rust preventive property, discoloration preventive property, and degreasing property With respect to white rust preventive property and discoloration preventive property, an increase in the amount of the inert type sulfur extreme pressure agent added is in a bad direction. Further, the highly basic sulfonate has an adverse effect on the anticorrosion property, especially the degreasing property of the iron surface (single-sided plated material), the alloying material, and the iron / zinc alloy material with the increase of the addition amount.

From the above, it was confirmed that the anti-sulfur property and the degreasing property also had an optimum balance point between the inert type sulfur extreme pressure agent and the highly basic sulfonate. (2) Structure of the present invention The present invention is a press working / cleaning rust preventive oil composition for cold rolled steel sheets and galvanized steel sheets.

The main constituents are (A) a lubricating base oil, (B) an alkaline earth metal salt or amine salt of an alkylsulfonic acid having a C of ₁₆ or more, a carboxylic acid having a C of ₁₂ or more, and C.
One or more anticorrosive additives selected from alkaline earth metal salts or amine salts of ₁₂ or more carboxylic acids, (C) an inert type sulfur-based extreme pressure agent, and (D) an alkali An oil-soluble sulfonic acid salt of an earth metal is mixed with a highly basic sulfonate containing an excessive amount of a hydroxide, oxide or carbonate of these metals, and the composition (A) is used with respect to the total amount of the composition. Lubricating base oil 65 to 85% by mass, (B) rust preventive additive 5 to 20% by mass, (C) inert type sulfur extreme pressure agent, and (D) oil-soluble sulfonate of alkaline earth metal 100 mass% in each range of 5 to 20 mass%
1 part by volume of the oil-soluble sulfonate of the alkaline earth metal (D) is added to 1 to 4 parts by volume of the inert type sulfur-based extreme pressure agent (C). And the viscosity of the composition at 40 ° C. is 1 mm ² / s or more
It is less than 10 mm ² / s and the total base number is 20 mgKOH / g or less.

In a preferred embodiment of the present invention, the inert type sulfur-based extreme pressure agent has a sulfur content of 15% or less and an active sulfur content of 5%.
% Or less, one or more selected from among sulfurized lard, sulfurized vegetable oil ester, and synthetic polysulfide, and the highly basic sulfonate is alkaline earth metal at least among Mg, Ca, and Ba. Contains one or more and has a total base number of 50 to 500 mg KOH / g
Is characterized in that.

[0036]

DETAILED DESCRIPTION OF THE INVENTION

1. Lubricating oil base oil As the lubricating oil base oil of the present invention, mineral oil or synthetic oil, or a mixture of mineral oil and synthetic oil can be used.

As the mineral oil, a combination of two or more light oil hydrocarbons and heavy oil hydrocarbons is usually used. The light oil hydrocarbons may be used alone without mixing with the heavy oil hydrocarbons.

Light oil hydrocarbons (high flash point solvent) are 4
It is preferable that the viscosity at 0 ° C. is 1 to 3 mm ² / s and the flash point is 70 ° C. or higher. It is also useful for dissolving the composition and adjusting the viscosity of the product, and does not adversely affect the function of other components even in the pressing process in the subsequent step.

The heavy oil hydrocarbons are preferably those from 80 neutral to 250 neutral fraction. 15
A 0 neutral fraction is more preferred. In the case of naphthenic mineral oil, a better one is used. In both cases, during the molding press working in the subsequent process, it works sufficiently as a base oil for the lubricating oil composition and continues to exist as a rust-preventing oil coating material.
It shall not adversely affect the degreasing property.

When the light oil hydrocarbons and the heavy oil hydrocarbons are used in combination, the blending ratio in the base oil is 85 to 100% by mass of the light oil hydrocarbons and the heavy oil hydrocarbons. 0 to
It is preferably 15% by mass.

Examples of the synthetic oil include poly-α-olefin, alkylbenzene, alkylnaphthalene, diester, polyol ester, polyphenyl ether and the like.

The blending ratio of the lubricating base oil to the total amount of the composition is 65 to 85% by mass.

When the lubricating base oil is less than 65% by mass,
The amount of rust preventive additive and extreme pressure agent forming the rust preventive oil film increases, and the oil film after oiling becomes rich in additive and has a high film thickness. It will also be adversely affected by the increase, adversely affecting degreasing and chemical conversion treatment. Further, if the lubricating base oil exceeds 85% by mass, the amount of the rust preventive additive compounded will be reduced, which will adversely affect the rust preventive property. Furthermore, since the compounding amount of the extreme pressure agent is also reduced, the press workability is also adversely affected. 2. In the rust additives present invention, as anti-rust additives, C ₁₆ or more alkaline earth metal salts or amine salts of alkyl sulfonic acids, C ₁₂ or higher carboxylic acids, C ₁₂ or more alkaline earth metal carboxylate One or more selected from salts and amine salts are used. These may be used alone or in combination.

Examples of the alkyl sulfonates (alkaline earth metal salts or amine salts of C ₁₆ or higher alkyl sulfonic acids) include alkylbenzene sulfonic acid, alkylnaphthalene sulfonic acid, and alkaline earth metal salts of petroleum sulfonic acid, Amine salts may be mentioned.

Examples of the carboxylic acid having C ₁₂ or more include oleyl sarcosinic acid and the like.

Examples of the carboxylic acid salt (alkaline earth metal salt or amine salt of C ₁₂ or more carboxylic acid) include:
Examples thereof include C ₁₂ or more carboxylic acids, oxidized waxes, alkaline earth metal salts of lanolin fatty acids, and amine salts. From the viewpoint of rust prevention and degreasing properties, sorbitan acid ester types include oleate, stearate, and laurate fatty acids.

It is preferable to use synthetic sulfonate Ba salt, oxidized wax Ba salt, and sorbitan fatty acid ester.

The proportion of the above-mentioned rust-preventive additive in the total amount of the composition is 5 to 20% by mass in view of the balance with other components.
Is.

If the amount of the rust preventive additive is less than 5% by mass, the rust preventive performance is adversely affected. This is because a dense adsorption film with a rust preventive additive, which is sufficient to protect the metal surface from corrosive substances and water containing the same, is not formed. Further, when the anticorrosive additive exceeds 20% by mass, the degreasing property is adversely affected. This is because the rust preventive performance and the degreasing performance of the rust preventive additive have a contradictory relationship also from the property of protecting the metal surface by the adsorbing ability of the additive. When it exceeds 20% by mass, the effect of adding the extreme pressure agent used in the present invention is suppressed. 3. Lubricity improver In the present invention,
The following mixture of the inert type sulfur extreme pressure agent and the highly basic sulfonate is used as a lubricity improver during press working, that is, a press workability improver.

When the inert type extreme sulfur pressure agent and the highly basic sulfonate are blended in an optimum ratio, they have the effect of improving press workability.

The blending ratio of the above mixture in the present composition is 5 to 20% by mass in view of the balance with other components. If it is less than 5% by mass, sufficient press working performance cannot be obtained. On the other hand, if it exceeds 20% by mass, rust prevention and degreasing properties are adversely affected. (1) Inactive type sulfur-based extreme pressure agent The inert type sulfur-based extreme pressure agent used in the present invention is obtained by sulfiding an unsaturated fat and oil, an unsaturated fatty acid and an olefin with mercaptan and hydrogen sulfide. , A compound having a sulfur bond.

A preferred embodiment thereof is at least one or more extreme pressure agents selected from sulfurized lard, sulfurized vegetable oil ester and synthetic polysulfide having a sulfur content of 15% or less and an active sulfur content of 5% or less. . These may be used alone or in combination. (2) Highly Basic Sulfonate The highly basic sulfonate used in the present invention is an alkaline earth metal oil-soluble sulfonate in which a hydroxide, oxide or carbonate of these metals is excessively contained. It is a thing.

In a preferred embodiment of the above-mentioned highly basic sulfonate, the alkaline earth metal contains at least one of Mg, Ca and Ba, and the total base number is 50 to 50.
500 mg KOH / g, preferably 300-400 mg
KOH / g. (3) Mixing ratio of inert type sulfur extreme pressure agent and highly basic sulfonate The mixing ratio of inert type sulfur extreme pressure agent and highly basic sulfonate is as follows. In order to prevent the plating film from peeling off, 1 to 4 parts by volume of the inert type sulfur-based extreme pressure agent is used as a highly basic sulfonate.
The capacity part.

The inert sulfur-based extreme pressure agent has a sulfurized vegetable oil ester having an active sulfur content of 3% by mass or less, a total base number of 300 mgKHO / g, and an alkaline earth metal of C.
It is more preferable to use the highly basic sulfonate of a, the compounding ratio is 1: 1, and the compounding amount is 8 to 12% by mass based on the total amount of the composition. 4. Viscosity of Composition and Total Base Number (1) Viscosity of Composition The composition of the present invention has a viscosity of 1 mm ² / s at 40 degrees.
It is an essential requirement that it is not less than 10 mm ² / s.

Since the present invention is a rust preventive oil composition for cleaning imparted with press workability, in addition to the basic three performance balances of rust preventive performance, degreasing performance, and processing performance, cleaning performance is required, and the product as a product is required. Appropriate viscosity is required.

When a mixture of light oil hydrocarbons and heavy oil hydrocarbons is used as a lubricating base oil, the composition has a viscosity of 1
When it is less than mm ² / s, the oiliness effect (viscosity effect) of heavy oil hydrocarbons (heavy oil base oil) forming a rust preventive oil film is adversely affected, and a film having a good film thickness is formed. Since it cannot be obtained, it also adversely affects rust prevention performance. Further, when the viscosity of the composition is 10 mm ² / s or more, the blending amount of the heavy oil base oil increases, or the heavy oil base oil further increases in viscosity, and the film thickness of the oil film increases, so The stickiness of the steel plate adversely affects the cleanability. The discoloration preventing property and the degreasing property are also physically adversely affected by increasing the film thickness and increasing the viscosity.

When only light oil hydrocarbons are used as the lubricating base oil, if the viscosity of the composition is less than 1 mm ² / s, the effect of the additive forming the rust preventive oil film is adversely affected. Further, when the viscosity of the composition is 10 mm ² / s or more, since the amount of the additive compounded is large, the film thickness of the oil film becomes large, which adversely affects the cleaning property, discoloration preventing property and degreasing property. (2) Total Base Number of Composition The total base number of the composition is required to be 20 mgKOH / g or less.

When the total base number of the composition exceeds 20 mgKOH / g, the highly basic sulfonate, which is a constituent of the present invention, adversely affects rust prevention and degreasing. 5. Other compoundable additives As long as the object of the present invention is achieved, a degreasing aid, an antioxidant, an oiliness agent, which is usually used as a cleaning rust preventive oil for cold-rolled steel sheets and galvanized steel sheets,
A water displacing agent and other additives can be appropriately blended.

[0059]

EXAMPLES Examples of the present invention and comparative examples will be described below. However, the present invention is not limited to these examples. 1. Composition Tables 1 and 2 show the compositions by mass% of Examples and Comparative Examples of the present invention.

Mineral oil having a viscosity of 2 mm ² / s at 40 ° C. was used as the light oil hydrocarbon of the base oil, and mineral oil having a viscosity of 25 mm ² / s at 40 ° C. was used as the heavy oil hydrocarbon.

Comparative Examples 8 and 9 are commercially available press-cleaning rust preventive oils applied to thin steel sheets for the automobile industry. Comparative Example 10 is a commercially available oil for cleaning rust preventive oil for the thin steel sheet.

[0062]

[Table 1]

[0063]

[Table 2]

2. Test results Table 3 shows the test results. The test method will be described later.

[0065]

[Table 3]

3. Evaluation (1) Examples 1 to 10 The examples are excellent in balance of rust prevention, discoloration prevention, degreasing, and lubricity (press workability). In particular, the press workability is good even under heating at 60 ° C., assuming an actual press work line. (2) Comparative Examples 1 and 2 Comparative Example 1 (50% by mass of lubricating base oil and 30% by mass of rust preventive additive) has good lubricity (press workability), but rust preventive property under eaves exposure conditions. , Inferior in discoloration preventing property and degreasing property.

Comparative Example 2 (88% by mass of lubricating base oil) is inferior in rust prevention and discoloration prevention under eaves exposure conditions. Also, 6
The lubricity (press workability) at 0 ° C. was 17.1 KN, which was below the target value of 19.0 KN.

From Comparative Examples 1 and 2 and Examples 1 and 5, it is understood that the blending ratio of the lubricating base oil of the present invention is preferably 65 to 85 mass%. (3) Comparative Examples 3 and 4 Comparative Example 3 (corrosion preventive additive 4% by mass) has good degreasing property and lubricity (press workability), but is inferior in rust preventive property and discoloration preventive property.

Comparative Example 4 (25% by mass of rust preventive additive) has a poor degreasing property.

From Comparative Examples 3 and 4 and Examples 6 and 7, it can be seen that the mixing ratio of the rust preventive additive of the present invention is preferably 5 to 20% by mass. (4) Comparative Examples 5 and 6 Comparative Example 5 (lubricity improver 4% by mass) has high lubricity (press workability) at room temperature (25 ° C.), high temperature (60 ° C.).
It is bad even under the conditions.

Comparative Example 6 (30% by mass of lubricity improver)
Good lubricity (press workability), but poor rust prevention, discoloration prevention and degreasing properties under eaves exposure conditions.

From Comparative Examples 5 and 6 and Examples 8 and 9, it is understood that the blending ratio of the mixture of the inert type sulfur extreme pressure agent of the present invention and the highly basic sulfonate is preferably 5 to 20% by mass. (5) Comparative Example 7 Comparative Example 7 (viscosity of the composition at 40 ° C. 11.0 mm ²
/ S) has good lubricity (press workability), but is inferior in discoloration preventing property and degreasing property.

From Comparative Example 7 and Example 10 (viscosity of the composition at 40 ° C. of 9.0 mm ² / s), it can be seen that the viscosity of the composition of the present invention at 40 ° C. is less than 10.0 mm ² / s. . (6) Comparative Examples 8 to 10 The commercially available rust preventive oil for cleaning and pressing (the active sulfur content of the composition is 0.8%) of Comparative Example 8 has rust preventive property, discoloration preventive property, degreasing property,
Lubricity (press workability) is all poor.

The commercially available rust preventive oil for press and cleaning of Comparative Example 9 (active sulfur content of the composition was not detected) was inferior in rust preventive property under eaves exposure conditions. Also, degreasing and high temperature (60 ℃)
Poor press workability under the conditions.

The rust preventive oil for cleaning of the commercial oil of Comparative Example 10 has good rust preventive property, discoloration preventive property, and degreasing property, but has no press workability, so that press workability is extremely poor. 4. Test method (1) Test steel plate Cold rolled steel plate: CR material Plate thickness 0.8 mm Alloyed hot-dip galvanized steel plate: GA material Plated thickness 60/6
0 (g / m ² ) plate thickness 0.75 mm Note that the test oil was applied by dipping on a test steel plate. (2) Rust prevention test 1) Wetting test a. Test steel plate: GA material Plating thickness 60/60 (g /
m ² ) Plate thickness 0.75 mm Dimensions 80 × 90 (cm) b. Test method: 240 according to JIS K 2246
The occurrence of white rust and red rust after the elapse of time was measured. c. Judgment: A grade; 0 to less than 1% B grade; 1% to less than 10% C grade; 10% to less than 25% D grade; 25% to less than 50% E grade; 50% to 2) Eaves exposure Test a. Test steel plate: CR material, plate thickness 0.8 mm, size 80 × 9
0 (cm) b. Test method: After dipping and applying oil, the one left for one day and night was exposed under the eaves, and the rust generation rate and the discoloration degree were evaluated on the 30th day of exposure. c. Judgment: Rust occurrence degree ○; None △; 0 to less than 10% ×; Discoloration degree of 10% or more ○; None △; Little discoloration ×; Significant discoloration (3) Degreasing test a. Test steel plate: GA material Plating thickness 60/60 (g /
m ² ) Plate thickness 0.75 mm Dimensions 80 × 90 (cm) b. Test method: After immersion and oiling, exposed for 1 week indoors, degreasing agent Fine Cleaner 4326T (manufactured by Nippon Parkerizing Co., Ltd.) was used to carry out alkaline degreasing by a spray degreasing method, and after washing with water for 30 seconds, an angle of 60 ° And the water-wetted area after a certain period of time was determined. c. Test conditions: temperature 45 ° C., concentration 2% time 30, 60, 90, 120 seconds d. Judgment: ◯; 98% or more of water was wet in 30 seconds.

Δ: 98% or more wet with water in 60 to less than 120 seconds.

×: 98% or more of water was wetted in 120 seconds. (4) Lubricity test (press workability test) High-speed deep drawing test a. Test steel plate: GA material Plating thickness 60/60 (g /
m ² ) Plate thickness 0.75 mm Diameter 84φ mm b. Testing machine: High-speed cylindrical deep-drawing testing machine (made by Tokyo Testing Machine) c. Test conditions: Jig Punch diameter: 40 mm Die diameter: 42.5 mm Punch layer radius: 4R Die layer radius: 8R Drawing ratio 2.1 Drawing speed 1.0 mm / s Wrinkle pressing force 4.2 KN to 50 KN Temperature room temperature (25 ° C ), 60 ° C. d. Judgment: Wrinkle presser load increases by 2.1 KN unit,
Maximum wrinkle holding force (KN) that did not cause breakage even once
Was set as the breaking limit and 19.0 KN or more was set as the target value.

[0078]

INDUSTRIAL APPLICABILITY The present invention is a lubricating oil composition for preparing a rust preventive oil for cleaning used in the automobile industry, the home appliance industry, etc., and is a cold rolled steel sheet and a galvanized steel sheet supplied from a steel manufacturer. It is a cleaning rust preventive oil composition for press working, which is easily washed to prevent rusting of molded parts and imparts press workability so that it can be used as it is in a molding press working step.

[0079] The compositions of the present invention has a viscosity at 40 ° C. of less than ^{1 mm} 2 / s or more to 10 mm ² / s, based on the new knowledge that we have obtained, lubricating base oil and rust additive, An inert type sulfur-based extreme pressure agent and a highly basic sulfonate are mixed in an optimum ratio.

Therefore, the present invention has excellent cleaning property, rust preventive property, discoloration preventive property, degreasing property, moldability, and especially press workability at high temperature due to these additive and synergistic effects.

In particular, regarding press workability, since press cracking prevention property and plating layer peeling prevention property are imparted, cleaning, rust prevention, discoloration prevention and press forming of galvanized steel sheet are performed with one type of lubricating oil. It is possible to obtain a finished product.

Further, by using the rust preventive oil for press working and cleaning prepared by the present invention, production in steel manufacturers, expansion of applications, simplification of process in automobile / home appliance industry, etc.
It greatly contributes to rationalization, improvement of productivity, improvement of quality of press-molded parts, resource saving, improvement of working environment.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C10M 159: 24) C10N 10:04 C10N 10:04 20:02 20:02 30:00 A 30:00 30:04 30:04 30:06 30:06 30:12 30:12 40:24 Z 40:24 (56) Reference JP 4-275399 (JP, A) JP 7-18281 (JP, A) JP 61 -26695 (JP, A) JP-A-5-339589 (JP, A) JP-A-2-270975 (JP, A) JP-A-62-297390 (JP, A) (58) Fields investigated (Int.Cl) . ^7, DB name) C10M 163/00 C10M 129/26 - 129/66 C10M 135/00 - 135/36 C10M 159/24 C10N 10:04 C10N 20:02 C10N 30:00 C10N 30:04 - 30:06 C10N 30:12 C10N 40:24

Claims (3)

(57) [Claims] 1. A (A) a lubricating base oil and, (B) C ₁₆ or more alkaline earth metal salts or amine salts of alkyl sulfonic acids, C ₁₂ or higher carboxylic acids, alkaline earth to C ₁₂ or more carboxylic acid One or more rust preventive additives selected from the group consisting of metal salts or amine salts, (C) an inert type sulfur extreme pressure agent, and (D) an oil-soluble sulfonic acid of an alkaline earth metal. The salt is prepared by blending a highly basic sulfonate in which a hydroxide, oxide or carbonate of these metals is excessively contained, and the above (A) lubricating base oil 65 to 85 mass relative to the total amount of the composition. %, 5 to 20% by mass of the (B) rust-preventive additive, 5 to 20% by mass of the mixture of the (C) inert type sulfur-based extreme pressure agent and (D) the oil-soluble sulfonate of an alkaline earth metal. Within the respective ranges of 100% by mass or less, and (C) 1 part by volume of the oil-soluble sulfonate of (D) an alkaline earth metal with respect to 1 to 4 parts by volume of an inert type sulfur extreme pressure agent, and the viscosity of the composition at 40 ° C. is 1 mm. ² / s or more to 10
A cold-rolled steel sheet and a galvanized steel sheet for press working and cleaning rust preventive oil composition, which has a total base number of less than mm ² / s and a total base number of 20 mgKOH / g or less. 2. An inert type sulfur-based extreme pressure agent having a sulfur content of 15
% Or less and an active sulfur content of 5% or less, and one or more selected from sulfurized lard, sulfurized vegetable oil ester, and synthetic polysulfide.
A cold-rolled steel sheet and a galvanized steel sheet for press working and cleaning rust preventive oil composition. 3. The alkaline earth metal contains at least one of Mg, Ca, and Ba, and is a highly basic sulfonate having a total base number of 50 to 500 mgKOH / g. A cold-rolled steel sheet and a galvanized steel sheet according to claim 1 or 2, wherein the press working / cleaning rust preventive oil composition is used.